Ultrasound assisted enzyme catalyzed synthesis of glycerol carbonate from glycerol and dimethyl carbonate

The present work illustrates the transesterification of glycerol to glycerol carbonate (GlyC) from dimethyl carbonate (DMC) using commercial immobilized lipase (Novozym 435) under ultrasonic irradiation. The experiments were performed in a batch reactor placed in an ultrasonic water bath using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound power on the conversion of glycerol to GlyC. It has been found that ultrasound-assisted lipase-catalyzed transesterification of glycerol would be a potential alternative to conventional alkali-catalyzed method, as high conversion (99.75%) was obtained at mild operating conditions: molar ratio of DMC to glycerol 3:1, catalyst amount of 13% (w/w), lower power input (100 W), duty cycle 50% and temperature (60 °C) in a relatively short reaction time (4 h) using Novozym 435 as catalyst. Ultrasound reduces the reaction time up to 4 h as compared to conventional stirring method (14 h) catalyzed by Novozym 435. The repeated use of the catalyst under the optimum experimental condition resulted in decay in both enzyme activity and product conversion.     

Moment analysis as a systematic tool for NMR powder pattern analysis

The low order moments for chemical shift and second-order quadrupolar powder patterns have been calculated as functions of the anisotropy and asymmetry parameter of the governing interaction, and the expressions inverted to give these parameters as a function of the moments. Theoretical simulations and experimental experience show that moment analysis in most cases equals and in some cases exceeds the accuracy of direct inspection as a method of obtaining NMR parameters. We illustrate the efficacy of the method applied to 31P chemical shift spectra of nucleic acids, and 39K second-order patterns of series of potassium salts.     

Rheological and NMR studies of polyethylene/calcium carbonate composites

Rheometry, 13C CP/MAS NMR spectra and 1H spin-lattice relaxation times T1 and T1rho have been employed to study the structure and molecular dynamics in composites of polyethylene (LDPE) with calcium carbonate filler. It has been found that the addition of the filler into the polymer leads to an increase in composite rigidity and a decrease in mobility in its crystalline regions. The presence of the filler affects the crystallization process making the crystal structure less perfect and reduces the size of the crystallites.     

Binary mixture of p‐methylbenzaldehyde with polar and nonpolar solvents

In this work, a combined theoretical and experimental study of binary mixture of liquid p‐methylbenzaldehyde (PMBz) is reported using ab initio calculations as well as Raman and IR spectroscopies. The purpose of this study was twofold: firstly, to describe the interaction of PMBz in terms of bonding energies and preferred geometries; and secondly, to characterize the spectroscopic effects on the vibrational modes of PMBz in the binary mixture of different polar and nonpolar solvents. The three vibrational modes, namely, carbonyl stretching, ν(C CH₃) and aldehydic (C H) vibrations have been analyzed in all the three solvents in different concentrations. The dependence of Raman linewidth on the concentration of PMBz of these modes was also taken into account. By analyzing the peak position and linewidth of these modes, it is seen that the solute–solvent interaction is stronger in BuOH and 1,2 dichloroethane (DCE) because of the hydrogen‐bonding interaction between these molecules. The formation of C H···O hydrogen bonds in liquid p‐methylbenzaldehyde is also investigated by Gaussian fitting. The ab initio calculations suggest several possible dimer configurations. Copyright © 2008 John Wiley & Sons, Ltd.     

A PFG NMR experiment for translational diffusion measurements in low-viscosity solvents containing multiple resonances

Pulsed gradient simulated-echo (PGSE) NMR diffusion measurements provide a facile and accurate means for determining the self-diffusion coefficients for molecules over a wide range of sizes and conditions. The measurement of diffusion in solvents of low intrinsic viscosity is particularly challenging, due to the persistent presence of convection. Although convection can occur in most solvent systems at elevated temperatures, in lower viscosity solvents (e.g., short chain alkanes), convection may manifest itself even at ambient laboratory temperatures. In most circumstances, solvent suppression will also be required, and for solvents that have multiple resonances, effective suppression can likewise represent a substantial challenge. In this article, we report an NMR experiment that combines a double-stimulated echo PFG approach with a WET-based solvent suppression scheme that effectively and simultaneously address the issues of dynamic range and the deleterious effects of convection. The experiment described will be of general benefit to studies aimed at the characterization of diffusion of single molecules directly dissolved in low-viscosity solvents, and should also be of substantial utility in studies of supramolecular assemblies such as reverse-micelles dissolved in apolar solvents.     

Modified z-gradient filtering as a mean to obtain phased deuterium autocorrelation 2D NMR spectra in oriented solvents

We describe a modified z-gradient filter scheme specifically designed to obtain pure absorption mode deuterium 2D NMR spectra recorded in oriented solvents. The proposed technique is investigated by analysing the evolution of the density operator for a spin I=1. The method is applied to the recently designed Q-COSY and Q-resolved 2D experiments to simplify the analysis of chiral molecules dissolved in weakly orienting chiral liquid crystals. The efficiency of this z-gradient filtering technique is illustrated using the perdeuterated 1-butanol, a prochiral molecule of average Cs symmetry, dissolved in an organic solution of poly-gamma-benzyl-L-glutamate (PBLG). The experimental results as well as the advantages of the new experiments compared with the previous ones are described and discussed.     

DFT study of solvation of Li~+/Na~+ in fluoroethylene carbonate/vinylene carbonate/ethylene sulfite solvents for lithium/sodium-based battery

Choosing suitable solvent is the key technology for the electrochemical performance of energy storage device.Among them,vinylene carbonate(VC),fluoroethylene carbonate(FEC),and ethylene sulfite(ES)are the potential organic electrolyte solvents for lithium/sodium battery.However,the quantitative relation and the specific mechanism of these solvents are currently unclear.In this work,density functional theory(DFT)method is employed to study the lithium/sodium ion solvation in solvents of VC,ES,and FEC.We first find that 4VC-Li+,4VC-Na+,4ES-Li+,4ES-Na+,4FEC-Li+,and 4FEC-Na+are the maximum thermodynamic stable solvation complexes.Besides,it is indicated that the innermost solvation shells are consisted of 5VC-Li+/Na+,5ES-Li+/Na+,and 5FEC-Li+/Na+.It is also indicated that the Li+solvation complexes are more stable than Na+complexes.Moreover,infrared and Raman spectrum analysis indicates that the stretching vibration of O=C peak evidently shifts to high frequency with the Li+/Na+concentration reducing in nVC-Li+/Na+and nFEC-Li+/Na+solvation complexes,and the O=C vibration peak frequency in Na+solvation complexes is higher than that of Li+complexes.The S=O stretching vibration in nES-Li+/Na+solvation complexes moves to high frequency with the decrease of the Li+/Na+concentration,the S=O vibration in nES-Na+is higher than that in nES-Li+.The study is meaningful for the design of new-type Li/Na battery electrolytes.     

反演与拟合相结合处理核磁共振弛豫数据的方法

讨论非负最小二乘（NNLS）法和非线性拟合在分析处理核磁共振（NMR）弛豫数据中的应用.同时将二者结合，提出用NNLS的反演结果来设定非线性拟合初值的方法，并用计算机模拟和实验证明了该方法在分析处理NMR弛豫数据中的有效性. 关键词： 非负最小二乘法 非线性拟合 核磁共振 弛豫时间     

A homodecoupled diffusion experiment for the analysis of complex mixtures by NMR

Diffusion ordered spectroscopy (DOSY) relies on differences in translation diffusion as a means to separate components in a solution mixture. However, the analysis of spectra of mixtures can be problematic because spectral overlap. It is the aim of this article to propose a pulse sequence and processing method that leads to a complete 2D homodecoupled-DOSY experiment. This experiment offers several advantages that could extend the range of applications to more complex mixtures by achieving important improvements in both signal dispersion and sensitivity.     

The Effectiveness of Glycerol Solutions for Optical Clearing of the Intact Skin as Measured by Confocal Raman Microspectroscopy

Optics and Spectroscopy - The effect of glycerol solutions of different concentrations and exposure times on the optical clearing efficiency in intact pig skin has been studied in the analysis of...     

采用CO2天然混合制冷剂的制冷系统热力学分析

受工况条件的限制,CO2制冷系统在实际应用中往往需要采用跨临界循环,高压侧压力高达10MPa及以上。高的运行压力对系统各部件、设备的安全运行均提出更高要求,从而造成初投资增大。采用CO2混合工质,可以有效地改善纯的CO2系统存在的不足。针对三组CO2天然混合工质——R744/R290、R744/R600、R744/R600 a,在特定的工况条件下,对制冷系统进行了热力学理论分析和计算。探讨了混合工质中CO2不同质量配比、不同蒸发器出口制冷剂温度对系统制冷量、COP和冷凝压力的影响。结果表明:在相同工况下,R744/R290的冷凝压力比R744R/600高12~23%,比R744/R600 a高19~24%;R744/R290的COP值比R744/R600高33~41%,比R744/R600 a高25~32%。     

Micropore size analysis by NMR in hydrated cement

The understanding of the microstructure of cement remains incomplete. Especially, the progressive setting of the material is still unclear. Micropore size distribution (microstructure) has been investigated by both standard proton nuclear magnetic relaxation (1H-NMR) and field-cycling relaxation in C3S hydrated paste. The non-exponential decay was interpreted as a distribution of discrete relaxation rates. The attribution of T1 is supported by both a spectral and a dispersion curve analyses. These experiments allow us to follow the structuration of the material during setting.     

混合工质HFC134a/HCs替代R502的性能分析

针对目前R502主流替代工质R507和R404A存在的温室效应指数高、与矿物油互溶性差等缺点,提出了环保性能更好的三组近共沸混合工质R134a/R290、R134a/R1270和R134a/R290/R1270作为R502新型替代工质;并对其热物性、循环性能、安全性能和溶油性进行了计算分析。结果表明：除了压缩机排气温度偏高,这三组R134a/HCs混合工质的其它主要循环性能参数如压缩机压力比、容积制冷量和系统性能系数COP都优于R507和R404A,并且从理论上讲不存在可燃可爆的危险,同时可以与矿物油互溶,在替代R502方面更具有优势,其中R134a/R290/R1270在高热负荷下的综合性能最优良。     

Crystallization of carboxylic acids as studied by NMR Spectrometry

The temperature dependences of the narrow ¹H NMR signals, in the temperature range below phase transition point from the plastic to brittle crystal for pivalic acid (PA) confined in the controlled pore size glasses with mean diameters of 7.9 and 23.9 nm have been investigated in order to determine the depression of the crystallization temperature and the pore size distribution parameters. The obtained parameters and the temperature dependences of the narrow ¹H NMR signals in the solid phases of PA and other carboxylic acids (hexadecanoic (C₁₆), heptadecanoic (C₁₇), octadecanoic (C₁₈), nonadecanoic (C₁₉)) have been used for studying the pore size distributions appeared during the natural crystallization. It was found that the pore size distribution for the even-numbered acids (C₁₆ and C₁₈) is spread over much wider range of the sizes comparing with those for odd-numbered acids (C₁₇ and C₁₉). The maximal value of the pore radius R?=?40.4 nm has been found at the temperature just below the melting point of C₁₈, which is about eight times bigger than that found for C₁₇.     

The ultrasound-assisted oxidative scission of monoenic fatty acids by ruthenium tetroxide catalysis: influence of the mixture of solvents

Carboxylic acids and diacids were synthesized from monoenic fatty acids by using RuO4 catalysis, under ultrasonic irradiation, in various mixtures of solvents. Ultrasound associated with Aliquat 336 have promoted in water, the quantitative oxidative cleavage of the CH=CH bond of oleic acid. A design of experiment (DOE) shows that the optimal mixture of solvents (H2O/MeCN, ratio 1/1, 2.2% RuCl3/4.1 eq. NaIO4) gives 81% azelaic acid and 97% pelargonic acid. With the binary heterogeneous mixture H2O/AcOEt, the oxidation of the oleic acid leads to a third product, the alpha-dione 9,10-dioxostearic acid.     

Molecular dynamics in comb-like ionene as studied by NMR

Proton and fluorine second moment and spin-lattice relaxation timesT ₁ andT _lρ have been employed to study molecular dynamics in the comb-like I-6,6-16-Me-BF₄ ionene in the temperature range from 110 up to 300 K. The existence of motions of methyl groups, trans-gauche isomerization, and/or rotation of the main- and side-chain méthylene groups, as well as isotropic reorientation of tetrafluoroborate ions were established. The observed relaxation behaviors are explained by motional models which assume Davidson-Cole asymmetrical distribution of correlation times. The best-fit motional parameters are given.